CN1623900A - Refining method and device for ammonia - Google Patents
Refining method and device for ammonia Download PDFInfo
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- CN1623900A CN1623900A CNA2004100617629A CN200410061762A CN1623900A CN 1623900 A CN1623900 A CN 1623900A CN A2004100617629 A CNA2004100617629 A CN A2004100617629A CN 200410061762 A CN200410061762 A CN 200410061762A CN 1623900 A CN1623900 A CN 1623900A
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C1/00—Ammonia; Compounds thereof
- C01C1/02—Preparation, purification or separation of ammonia
- C01C1/024—Purification
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D1/00—Evaporating
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D5/00—Condensation of vapours; Recovering volatile solvents by condensation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/26—Drying gases or vapours
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- Drying Of Gases (AREA)
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- Vaporization, Distillation, Condensation, Sublimation, And Cold Traps (AREA)
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Abstract
The object of this invention is to provide an ammonia refining method for efficiently removing diversified kinds of non-metallic impurities included in raw material ammonia and simplifying a continuous refining process, and to provide an apparatus therefor. The gaseous ammonia refining apparatus of this invention refines the crude gaseous ammonia containing moisture and low boiling point gaseous impurities having a boiling point lower than that of the ammonia, and is equipped with: a distillation section 3 which consists of a heat exchanger into which the crude gaseous ammonia is introduced to liquefy the gaseous ammonia by using a cooling effect; an exhaust path which is disposed in the distillation section 3 and exhausts the low boiling point gaseous impurities in a gaseous state; a vaporizer which vaporizes the liquefied ammonia discharged from the distillation section 3; moisture adsorption sections 22 and 24 which adsorb the moisture; catalyst sections 23 and 25 which separate oxygen; and a gaseous ammonia introducing path which introduces the gaseous ammonia vaporized by the vaporizer into the moisture adsorption sections 22 and 24 and the catalyst sections 23 and 25.
Description
Technical Field
The present invention relates to a purification method for purifying a crude ammonia gas containing various impurities, and more particularly, to an ammonia purification method and a purification apparatus for supplying a high-purity ammonia gas required in the semiconductor industry, the chemical industry, the research institute, and the like.
Background
Ammonia is generally used in the semiconductor manufacturing industry and the like, and ammonia purified from raw ammonia is used in the manufacturing site. The raw material ammonia is ammonia synthesized in an ammonia production plant, or recovered ammonia recovered from a use site, or the like. This raw material ammonia contains, in addition to metals, water, hydrogen, oxygen, carbon monoxide, carbon dioxide, and non-metallic impurities such as methane, and it is necessary to purify the ammonia to a high purity for use in semiconductor production or the like.
In the past, various studies have been made to remove impurities contained in the above-mentioned raw material ammonia. For example, in order to remove moisture, patent document 1-Japanese patent application laid-open No. 9-142833 discloses a method of removing ammonia by bringing it into contact with barium oxide. Further, patent document 2-Japanese unexamined patent publication No. 6-107412 discloses a method for removing carbon monoxide and carbon dioxide by bringing ammonia into contact with a nickel catalyst.
However, as described above, since the raw material ammonia contains a plurality of impurities, it is necessary to carry out a separate substance removal method proposed in patent document 1, patent document 2, or the like. Therefore, the productionof purified ammonia requires many purification steps. That is, in order to efficiently obtain a large amount of high-purity ammonia, continuous purification is required. When there are many individual purification steps, there is a problem that a large-scale purification facility is required for continuous purification.
Disclosure of Invention
The 1 st object of the present invention is to provide an ammonia purification method and an ammonia purification apparatus which can efficiently remove a plurality of non-metallic impurities contained in raw material ammonia without using a multi-step purification process. Further, the 2 nd object is to provide a method for purifying ammonia and a purification apparatus therefor, which can remove impurities such as water and oxygen with high efficiency and contribute to continuous purification with high efficiency. Further, the 3 rd object is to provide an ammonia purification method and purification apparatus which can efficiently remove a plurality of kinds of non-metallic impurities, purify high-purity ammonia, and simplify a continuous purification process.
The present invention has been made to solve the above problems, and a 1 st aspect of the present invention is a method for purifying a crude ammonia gas containing a low-boiling impurity gas having a lower boiling point than ammonia, the method comprising: after the crude ammonia gas is introduced into a distillation unit constituted by a heat exchanger, the ammonia gas is liquefied by the cooling action of the heat exchanger, and the low-boiling impurity gas is directly discharged in a gaseous state from the distillation unit, thereby removing the low-boiling impurity gas from the crude ammonia gas.
The invention according to claim 2 is the method for purifying ammonia gas according to claim 1, wherein a liquefied ammonia storage unit for storing liquefied ammonia is provided in the distillation unit, and the liquefied ammonia in the liquefied ammonia storage unit is heated to exhaust gas to remove low-boiling impurities remaining in the liquefied ammonia.
The 3 rd aspect of the present invention is the method for purifying ammonia gas according to the 1 st or 2 nd aspect, wherein the liquefied ammonia is discharged from the liquefied ammonia storage unit and vaporized by passing through a heating unit.
The 4 th aspect of the present invention is a method for purifying a crude ammonia gas containing at least water and oxygen, comprising introducing the crude ammonia gas into a water adsorption unit that adsorbs water and a catalyst unit that separates oxygen, and removing water and oxygen from the crude ammonia gas.
The 5 th aspect of the present invention is a method for purifying a crude ammonia gas containing at least water and oxygen, comprising providing at least a pair of a water adsorption section for adsorbing water and a catalyst section for separating oxygen, wherein the crude ammonia gas is introduced into one of the water adsorption section and the catalyst section to remove water and oxygen from the crude ammonia gas, and a reducing gas is introduced into the other of the water adsorption section and the catalyst section to regenerate the crude ammonia gas.
The 6 th aspect of the present invention is the method for purifying ammonia gas according to the 5 th aspect, wherein the moisture and oxygen in the crude ammonia gas are removed and the crude ammonia gas is continuously purified by regeneration by introducing the reducing gas, alternately and repeatedly, for each of the pair of the moisture adsorbing portion and the catalyst portion.
The 7 th aspect of the present invention is a method for purifying a crude ammonia gas containing moisture and a low-boiling impurity gas having a lower boiling point than ammonia, comprising a first removal step, a gasification step and a second removal step, in the first removal step, the crude ammonia gas is introduced into a distillation unit comprising a heat exchanger, the ammonia gas is liquefied by the cooling action of the heat exchanger, the low-boiling impurity gas is directly discharged from the distillation unit in a gaseous state, and the low-boiling impurity gas is removed from the crude ammonia gas, in the gasification step, the ammonia liquefied in the distillation unit is discharged from the distillation unit, passed through a heating unit, and gasified, in the second removal step, the ammonia gas vaporized in the vaporization step is introduced into the moisture adsorption section that adsorbs moisture and the catalyst section that separates oxygen, and water and oxygen are removed from the ammonia gas.
An 8 th aspect of the present invention is the method for purifying ammonia gas according to the 7 th aspect, wherein the method comprises a third removal step of providing a liquefied ammonia storage unit for storing the ammonia liquefied in the first removal step, removing low boiling point impurities remaining in the liquefied ammonia by discharging the liquefied ammonia stored in the liquefied ammonia storage unit by heating the liquefied ammonia, and introducing the liquefied ammonia to the gasification step by the third removal step to gasify the liquefied ammonia.
The 9 th aspect of the present invention is the ammonia purification method according to the 7 th or 8 th aspect, wherein the second removal step includes a removal treatment in which ammonia gas vaporized in the gas step is introduced into one of the moisture adsorption section and the catalyst section provided with at least one pair of the moisture adsorption section and the catalyst section to remove water and oxygen from the ammonia gas, and a regeneration treatment in which a reducing gas is introduced into the other of the moisture adsorption section and the catalyst section to regenerate the ammonia gas.
A 10 th aspect of the present invention is the method for purifying ammonia gas according to the 9 th aspect, wherein the removal treatment of moisture and oxygen and the regeneration treatment by introducing the reducing gas are alternately repeated for each of the pair of the moisture adsorbing portion and the catalyst portion to perform continuous purification.
An 11 th aspect of the present invention is the ammonia gas purification method according to any one of the 1 st to 10 th aspects, wherein the crude ammonia gas is a gas-phase component gas obtained by separating a raw material ammonia into a liquid phase and a gas phase.
The 12 th aspect of the present invention is a purification apparatus for purifying a crude ammonia gas containing a low-boiling impurity gas having a boiling point lower than that of ammonia, comprising a distillation section comprising a heat exchanger for liquefying ammonia gas by a cooling action after introducing the crude ammonia gas, wherein the distillation section is provided with an exhaust passage for directly exhausting the low-boiling impurity gas in a gaseous state.
The 13 th aspect of the present invention is the ammonia gas purification apparatus according to the 12 th aspect, wherein the distillation unit includes a liquefied ammonia storage unit for storing liquefied crude ammonia, and a heating device for separating the low-boiling impurity gas from the liquefied ammonia in the liquefied ammonia storage unit.
The 14 th aspect of the present invention is the ammonia purification apparatus according to the 12 th or 13 th aspect, wherein a vaporizer is provided for vaporizing the liquefied ammonia discharged from the distillation section.
The 15 th aspect of the present invention is a purification apparatus for purifying a crude ammonia gas containing at least water and oxygen, comprising a water adsorption section for adsorbing water and a catalyst section for separating oxygen, wherein the crude ammonia gas is introduced into the water adsorption section and the catalyst section to remove water and oxygen from the crude ammonia gas.
The 16 th aspect of the present invention is a purification apparatus for purifying a crude ammonia gas containing at least water and oxygen, comprising at least a pair of a water adsorption section for adsorbing water and a catalyst section for separating oxygen, wherein a crude ammonia gas introduction passage for introducing the crude ammonia gas into each of the water adsorption section and the catalyst section and a reducing gas introduction passage for introducing a reducing gas into each of the water adsorption section and the catalyst section are provided, the crude ammonia gas is introduced into one of the water adsorption section and the catalyst section through the crude ammonia gas introduction passage to remove water and oxygen from the crude ammonia gas, and the reducing gas is introduced into the other of the water adsorption section and the catalyst section through the reducing gas introduction passage to regenerate the crude ammonia gas.
A 17 th aspect of the present invention is the ammonia gas purification apparatus according to the 16 th aspect, comprising a continuous purification control unit for controlling opening and closing of the crude ammonia gas introduction passage and the reducing gas introduction passage, wherein the moisture adsorption unit and the catalyst unit in a pair alternately repeat removal of moisture and oxygen from the crude ammonia gas and regeneration of the reducing gas introduced thereto.
The 18 th aspect of the present invention is a purification apparatus for purifying a crude ammonia gas containing moisture and a low-boiling impurity gas having a boiling point lower than that of ammonia, comprising a distillation section comprising a heat exchanger for introducing the crude ammonia gas and liquefying the ammonia gas by a cooling action, an exhaust passage provided in the distillation section for directly exhausting the low-boiling impurity gas in a gaseous state, a vaporizer for vaporizing the liquefied ammonia discharged from the distillation section, a moisture adsorption section for adsorbing moisture, a catalyst section for separating oxygen, and an ammonia gas introduction passage for introducing the ammonia gas vaporized by the vaporizer into the moisture adsorption section and the catalyst section.
A 19 th aspect of the present invention is the ammonia purification apparatus according to the 18 th aspect, wherein the distillation unit is provided with a liquefied ammonia storage unit for storing crude ammonia liquefied by the distillation unit, and the liquefied ammonia storage unit includes a heating device for separating low-boiling impurities from liquefied ammonia remaining in the liquefied ammonia storage unit.
A 20 th aspect of the present invention is the ammonia purification apparatus according to the 18 th or 19 th aspect, wherein the apparatus comprises at least one pair of the moisture adsorbing portion and the catalyst portion, the ammonia gas introducing passage for introducing the ammonia gas gasified by the gasifying device is provided in each of the moisture adsorbing portion and the catalyst portion, the reducing gas introducing passage for introducing a reducing gas is provided in each of the moisture adsorbing portion and the catalyst portion, the gasified ammonia gas is introduced into one of the moisture adsorbing portion and the catalyst portion through the ammonia gas introducing passage to remove water and oxygen from the ammonia gas, and the reducing gas is introduced into the other of the moisture adsorbing portion and the catalyst portion through the reducing gas introducing passage to regenerate the ammonia gas.
A 21 st aspect of the present invention is the ammonia purification apparatus according to the 20 th aspect, wherein a continuous purification control unit that controls opening and closing of the ammonia introduction passage and the reducing gas introduction passage is provided, and the moisture and oxygen removal of the crude ammonia gas and the regeneration by the introduction of the reducing gas are alternately repeated for each of the pair of the moisture adsorption unit and the catalyst unit.
The 22 nd aspect of the present invention is the ammonia gas purification apparatus according to any one of the 12 th to 21 th aspects, wherein the crude ammonia gas is a gas-phase component gas obtained by separating a raw material ammonia into a liquid phase and a gas phase.
In the method for purifying ammonia gas according to claim 1 of the present invention, the crude ammonia gas is introduced into a distillation unit constituted by a heat exchanger, the ammonia gas is liquefied by the cooling action of the heat exchanger, and the low boiling point impurity gas having a boiling point lower than that of ammonia is directly discharged from the distillation unit in a gaseous state, thereby removing the low boiling point impurity gas from the crude ammonia gas.
The crude ammonia gas in the present invention is raw ammonia in a gaseous state. The low-boiling impurity gas having a boiling point lower than that of ammonia is hydrogen (H) contained in the crude ammonia gas2) Oxygen (O)2) Carbon monoxide (CO) and carbon dioxide (CO)2) Nitrogen (N)2) Methane (CH)4) And the like.
In the purification method according to claim 2 of the present invention, in the above-mentioned claim 1, the distillation unit is provided with a liquefied ammonia storage unit for storing liquefied ammonia, and liquefied ammonia in the liquefied ammonia storage unit is heated, whereby low-boiling impurities remaining in the liquefied ammonia can be removed by exhausting gas, and ammonia of higher purity can be purified.
According to the purification method of claim 3 of the present invention, in the above-mentioned aspect 1 or 2, since the liquefied ammonia is discharged from the liquefied ammonia storage unit and then vaporized by the heating unit, the highly purified ammonia of the above-mentioned aspect 1 or 2 can be discharged in a gaseous state and supplied to the continuous step.
In the purification method according to claim 4 of the present invention, the crude ammonia gas is introduced into the moisture adsorption section for adsorbing moisture and the catalyst section for separating oxygen, and at least moisture and oxygen as non-metallic impurities are removed from the crude ammonia gas. In addition, when the catalyst portion of the present invention uses a nickel catalyst, not only oxygen but also carbon monoxide (CO) can be removed. The use of the nickel catalyst also exerts the same removal effect in the catalyst portion of the following embodiment of the present invention. The moisture adsorbent used in the moisture adsorption section of the present invention is preferably a molecular sieve, activated alumina, or the like.
In the purification method according to claim 5 of the present invention, at least a pair of a moisture adsorption section for adsorbing moisture and a catalyst section for separating oxygen is provided, and crude ammonia gas is introduced into one of the moisture adsorption section and the catalyst section to remove at least moisture and oxygen as non-metallic impurities from the crude ammonia gas, while a reducing gas is introduced into the other of the moisture adsorption section and the catalyst section to regenerate the crude ammonia gas. As the reducing gas used for regeneration, a mixed gas of hydrogen and nitrogen or a mixed gas of hydrogen and self-purified ammonia gas is used.
In the purification method according to claim 6 of the present invention, in the above-mentioned 5, the removal of moisture and oxygen from the crude ammonia gas and the regeneration by the introduction of the reducing gas are alternately repeated for each of the pair of the moisture adsorption section and the catalyst section, and the purification is continuously performed, so that a large amount of high-purity ammonia can be purified.
In the purification method according to claim 7 of the present invention, since the purification method comprises a first removal step of introducing a crude ammonia gas containing water and a low-boiling impurity gas having a lower boiling point than ammonia into a distillation unit constituted by a heat exchanger, liquefying ammonia gas by a cooling action of the heat exchanger, directly exhausting the low-boiling impurity gas in a gaseous state from the distillation unit, and removing the low-boiling impurity gas from the crude ammonia gas, a gasification step of exhausting the ammonia liquefied in the distillation unit from the distillation unit, and gasifying the ammonia gas by passing through a heating unit, and a second removal step of introducing the ammonia gas gasified in the gasification step into a water adsorption unit adsorbing water and a catalyst unit separating oxygen, and removing water and oxygen from the ammonia gas, the low-boiling impurity gas having a lower boiling point than ammonia can be removed by the first removal step, further, water and oxygen can be removed by the second removal step through the gasification step, whereby a continuous treatment step of impurities can be realized, and ammonia with higher purity can be purified.
In the purification method according to claim 8 of the present invention, the 7 th aspect includes a liquefied ammonia storage unit for storing the ammonia liquefied in the first removal step, a third removal step for removing low-boiling impurities remaining in the liquefied ammonia by heating the liquefied ammonia in the liquefied ammonia storage unit and exhausting the gas, and the liquefied ammonia is introduced into the gasification step and gasified in the third removal step, so that the low-boiling impurities remaining in the first removal step can be removed in the third removal step, and the purification purity can be improved.
In the purification method according to claim 9 of the present invention, in the aspect 7 or 8, the second removal step includes a removal process of introducing the ammonia gas vaporized in the vaporization step into one of the moisture adsorption section and the catalyst section provided with at least one pair of the moisture adsorption section and the catalyst section to remove water and oxygen from the ammonia gas, and a regeneration process of introducing a reducing gas into the other of the moisture adsorption section and the catalyst section to regenerate the ammonia gas, so that the purification can be continuously performed by performing the regeneration process of at least one of the moisture adsorption section and the catalyst section in the second removal step without interrupting the continuous process from the first removal step to the second removal step by the regeneration operation.
In the purification method according to claim 10 of the present invention, in the above-mentioned 9, continuous purification is carried out by alternately repeating the removal treatment of water and oxygen and the regeneration treatment by introducing a reducing gas to each of the pair of the water-adsorbing portion and the catalyst portion, so that a large amount of high-purity ammonia can be purified.
In the purification method according to claim 11 of the present invention, since the crude ammonia gas is a gas-phase component gas obtained by separating the raw material ammonia into a liquid phase and a gas phase, the properties of the liquid phase containing a large amount of moisture and metallic impurities are utilized, and the purification treatment is performed by performing the purification method according to any one of claims 1 to 10 on the gas-phase ammonia containing a very small amount of moisture and metallic impurities as a starting material for purification, whereby ammonia having a higher purity can be purified.
In the ammonia gas purification apparatus according to claim 12 of the present invention, the crude ammonia gas is introduced into the distillation unit constituted by the heat exchanger, the ammonia gas is liquefied by the cooling action of the heat exchanger, and the low boiling point impurity gas having a boiling point lower than that of ammonia is directly discharged in a gaseous state from the distillation unit through the exhaust passage, whereby the low boiling point impurity gas can be removed from the crude ammonia gas.
In the purification apparatus according to claim 13 of the present invention, in the aforementioned 12 th aspect, the distillation unit is provided with a liquefied ammonia storage unit for storing liquefied ammonia, and liquefied ammonia in the liquefied ammonia storage unit is heated by the heating device, whereby low-boiling impurities remaining in the liquefied ammonia can be removed from the exhaust gas, and ammonia of higher purity can be purified.
In the purification apparatus according to claim 14 of the present invention, since the liquefied ammonia is dischargedfrom the liquefied ammonia storage unit and then vaporized by the vaporizer, the purified ammonia of high purity can be discharged in a gaseous state in the aspect of 12 or 13, and can be supplied to the continuous step.
In the purification apparatus according to claim 15 of the present invention, the crude ammonia gas is introduced into the moisture adsorption unit for adsorbing moisture and the catalyst unit for separating oxygen, and at least moisture and oxygen as non-metallic impurities are removed from the crude ammonia gas.
In the purification apparatus according to the 16 th aspect of the present invention, at least a pair of a moisture adsorption section for adsorbing moisture and a catalyst section for separating oxygen is provided, crude ammonia gas is introduced into one of the moisture adsorption section and the catalyst section through the crude ammonia gas introduction passage to remove at least moisture and oxygen as nonmetallic impurities from the crude ammonia gas, and a reducing gas is introduced into the other of the moisture adsorption section and the catalyst section through the reducing gas introduction passage to regenerate the crude ammonia gas.
In the purification apparatus according to claim 17 of the present invention according to claim 16, the continuous purification control unit controls opening and closing of the crude ammonia gas introduction passage and the reducing gas introduction passage, whereby continuous purification can be performed by alternately repeating removal of moisture and oxygen from the crude ammonia gas and regeneration of the introduced reducing gas for each of the pair of the moisture adsorption unit and the catalyst unit, thereby purifying a large amount of high-purity ammonia.
In the purification apparatus according to claim 18 of the present invention, the crude ammonia gas containing water and the low-boiling impurity gashaving a lower boiling point than ammonia is liquefied by the distillation section and the exhaust passage provided in the distillation section and exhausting the low-boiling impurity gas in a gaseous state as it is, and the low-boiling impurity gas can be exhausted in a gaseous state as it is from the distillation section.
In the purification apparatus according to claim 19 of the present invention, in the above-mentioned 18 th aspect, a liquefied ammonia storage unit for storing liquefied ammonia is provided, and liquefied ammonia in the liquefied ammonia storage unit is heated by using the heating apparatus, whereby low-boiling impurities remaining in the liquefied ammonia can be separated and removed, and thus purification purity can be improved.
In the purification apparatus according to claim 20 of the present invention, in the above-mentioned 18 th or 19 th aspect, the ammonia gas gasified by the gasification apparatus is introduced into at least one of the moisture adsorption section and the catalyst section provided with the pair of the moisture adsorption section and the catalyst section through the ammonia gas introduction passage to remove water and oxygen from the ammonia gas, and the reducing gas is introduced into the other of the moisture adsorption section and the catalyst section through the reducing gas introduction passage to regenerate the ammonia gas, so that the regeneration process of the other of the moisture adsorption section and the catalyst section can be performed in parallel with the removal process of the one of the moisture adsorption section and the catalyst section, and the purification can be continuously performed without interrupting the removal process by the regeneration operation.
In the purification apparatus according to claim 21 of the present invention, in the 20 th aspect, the continuous purification control unit controls opening and closing of the crude ammonia gas introduction passage and the reducing gas introduction passage, so that the moisture and oxygen of the crude ammonia gas can be alternately and repeatedly removed and the reducing gas can be introduced into each of the pair of the moisture adsorption unit and the catalyst unit to continuously purify the crude ammonia gas, thereby achieving a large amount of high-purity ammonia.
In the 22 nd aspect of the present invention, since the crude ammonia gas is a gas-phase component gas obtained by separating the raw material ammonia into a liquid phase and a gas phase, the properties of the liquid phase containing a large amount of moisture and metallic impurities are utilized, and the gas-phase ammonia containing a very small amount of moisture and metallic impurities is used as a purification starting material, and the purification treatment is performed by the purification method of any one of the 12 th to 21 st aspects, whereby ammonia having a higher purity can be purified.
Drawings
FIG. 1 is a schematic configuration diagram of a purification apparatus of the present invention.
FIG. 2 is a schematic configuration diagram of another purification apparatus of the present invention.
FIG. 3 is a schematic configuration diagram of still another purification apparatus according to the present invention.
FIG. 4 is an analysis chart of impurity concentrations for explaining the purification effect of the present invention.
FIG. 5 is a graph showing a distribution of the amount of ammonia and the water concentration in the gas phase, which shows a suitable usage state of ammonia in the purification apparatus shown in FIG. 3.
Detailed Description
Hereinafter, embodiments of the ammonia purification method and purification apparatus according to the present invention will be described in detail with reference to the drawings.
The purification apparatus and the purification method for removing low-boiling impurities from crude ammonia according to the present invention will be described with reference to fig. 1. FIG. 1 is a schematic configuration diagram of a purification apparatus according to the present embodiment. Raw ammonia is charged in the liquid ammonia container 1, and the ammonia gas in the gas phase section 12 becomes crude ammonia gas for purification. The raw material ammonia is separated into the liquid phase portion 11 and the gas phase portion 12, and the liquid phase and the gas phase are separated, so that moisture and metallic impurities contained in the raw material ammonia remain substantially in the liquid phase portion 11. Therefore, the ammonia in the gas phase section 12 obtained by the liquid-phase/gas-phase separation is in a state where moisture and metal impurities are preliminarily removed, and therefore, the ammonia is transferred to the purification step in this state, and is a raw material suitable for higher-purity purification as a starting material ammonia.
A distillation column 2 for removing a plurality of kinds of non-metallic impurities contained in a crude ammonia gas is composed of a distillation section 3 composed of a heat exchanger 31 provided at the upper part of the column, a gas inflow section 7 provided at the middle part, and a liquefied ammonia storage section 8 provided at the lower part. The heat exchanger 31 of the distillation unit 3 is connected to the refrigerant circulation device 4 via the refrigerant supply circulation passages 41 and 42, and circulates and supplies the refrigerant to the heat exchanger 31. The refrigerant is ethylene glycol or the like, and the inside of the heat exchanger 31 is maintained at-5 ℃ to +10 ℃ by a temperature sensor monitoring system (not shown) provided in the refrigerant circulation device 4. A plurality of gas passages 32 of the heat exchanger 31 are formed in communication between the gas inflow portion 7 and the uppermost space 6 of the distillation column 2. The gas inflow portion 7 communicates with the gas phase portion 12 of the liquid ammonia container 1 through the gas supply passage 9, and the crude ammonia gas from the gas phase portion 12 is supplied through the gas supply passage 9. Since the crude ammonia gas supplied to the gas inflow portion 7 enters the gas passage 32 and is liquefied by the cooling action of the heat exchanger 31 and the refrigerant circulation device 4, droplets of the crude ammonia gas are formed in the liquefied ammonia storage portion 8 at the lowermost portion of the distillation column 2 and fall down, and liquefied ammonia is stored. On the other hand, when the crude ammonia in the distillation section 3 is liquefied in the uppermost space 6, the impurity gas having a low boiling point is accumulated together with a part of the ammonia gas, and is exhausted by an exhaust device (not shown) through the exhaust passage 10 provided in the uppermost space 6, so that the impurity gas can be discharged. At this time, the impurity gas accumulated in the uppermost space 6 is mainly hydrogen (H)2) Oxygen (O)2) Carbon monoxide (CO) and carbon dioxide (CO)2) Nitrogen (N)2) Methane (CH)4) And the like.
In the distillation unit 3, the crude ammonia gas is liquefied, the liquefied ammonia 81 is stored in the liquefied ammonia storage unit 8, and the nonmetallic impurities having a lower boiling point than ammonia are separated as a gas, so that the impurity gas can be separated and recovered in the uppermost space 6, and various impurities can be removed at once. Therefore, a separate removal step of impurities such as hydrogen, oxygen, carbon monoxide, carbon dioxide, nitrogen, and methane is not required, and the purification of ammonia can be easily and efficiently achieved by using the single distillation column 2.
The distillation column 2 also has a residual impurity exhaust function for achieving high purification of ammonia. That is, the liquefied ammonia storage unit 8 is provided with a hot water circulation pipe 13 for circulating the hot water supplied from the hot water circulation device 5 through the storage unit. The hot water is maintained at 30 to 50 ℃ by a temperature sensor monitoring system (not shown) provided in the hot water circulating device 5, and boiling (vaporization) occurs on the surface of the hot water circulating pipe 13 by this hot water circulation. Therefore, impurities remaining when the crude ammonia is liquefied in the distillation unit 3 are separated from the liquid ammonia, discharged to the gas inflow unit 7 side, and finally recovered in the uppermost space 6.
Since the heating function of the heating device constituted by the hot water circulating device 5 and the hot water circulating pipe 13 is provided to the liquefied ammonia storage unit 8, impurities remaining in the ammonia liquefied by the distillation unit 3 can be removed, and the purification purity of the ammonia can be further improved.
The liquid ammonia stored in the liquefied ammonia storage unit 8 is discharged to the vaporization unit 15 side through the discharge passage 14. The vaporizing section 15 is disposed in a warm water tank 16. A heater 18 is provided in the warm water tank 16, and the state of warm water at 30 to 100 ℃ is controlled by a constant temperature control unit 17. Therefore, the liquid ammonia discharged through the discharge passage 14 is returned to a gaseous state by the vaporization action of the vaporizing device constituted by the warm water tank 16 in the vaporizing section 15. The purified ammonia gas thus regasified can be discharged through the vaporizing section 15 by an exhaust device (not shown), and high-purity ammonia gas can be obtained.
Hereinafter, a purification apparatus and a purification method thereof capable of efficiently removing moisture and oxygen contained in crude ammonia will be described with reference to fig. 2. FIG. 2 is a schematic configuration diagram of a purification apparatus according to the present embodiment. The purification apparatus of the present embodiment is composed of a pair of water, oxygen and carbon monoxide removing sections 20 and 21. The water, oxygen and carbon monoxide removing sections 20 and 21 respectively include a water removing section 22 and a catalyst section 23, and a water removing section 24 and a catalyst section 25. The moisture removing parts 22 and 24 are filled with a molecular sieve composed of crystalline zeolite which adsorbs moisture. The moisture removing units 22 and 24 remove moisture by adsorption of a molecular sieve. As the moisture adsorbent, in addition to the molecular sieve, a moisture adsorbent such as activated alumina may be used. The catalyst portions 23 and 25 are filled with a nickel catalyst. The catalyst portions 23 and 25 adsorb and remove oxygen and carbon monoxide by the chemisorption action of the nickel catalyst. The removal of oxygen and carbon monoxide impurities by a nickel catalyst proceeds by the following chemical reaction.
The water, oxygen and carbon monoxide removing portions 20 and 21 each have a 2-layer separation structure of the water removing portion and the catalyst portion. For example, the ammonia purification amount is set to 3N (standard condition) m3At the time of the reaction, 0.3kg of a molecular sieve (filling height: 300mm) was filled in each moisture-removed part in a cylinder having an inner diameter of 43 mm. Each catalyst part was filled with 0.8kg of a nickel catalyst (filling height: 500 mm). In addition, in these moleculesWhen ammonia gas was introduced at a flow rate of 0.17m/s in a state where the sieve and the nickel catalyst were packed, the contact time with each adsorbent in the catalyst portion and the moisture removing portion was about 3 seconds and 1.77 seconds. The same adsorption effect can be obtained by using a single mixed structure in which the water, oxygen, and carbon monoxide removing portions 20 and 21 are mixed with the nickel catalyst.
The water, oxygen, and carbon monoxide removing units 20 and 21 introduce gaseous ammonia gas from the liquid ammonia tank 50 through the crude ammonia gas introduction passage 51 and the introduction passages 29 and 30, respectively. The liquid ammonia container 50 has the same configuration as the liquid ammonia container 1 used in the embodiment of fig. 1, and uses, as a gas to be purified, gaseous ammonia gas having a small amount of moisture and metal impurities, which is obtained by separating a liquid phase and a gaseous phase of raw ammonia.
In this apparatus, the flow directions of the gases in the purification step (lower → upper) and the regeneration step (upper → lower) are designed to be opposite. However, the regeneration step may be performed by using the lower portion → the upper portion, as in the purification step. Reference numerals 56, 58, and 59 denote gas introduction-side switching valves for ammonia gas to the water, oxygen, and carbon monoxide removal units 20 and 21. The regeneration gas composed of the hydrogen reducing gas supplied from the regeneration gas supply devices 54 and 55 passes through the regeneration gas introduction passage and is supplied to the respective water, oxygen, and carbon monoxide removing units 20 and 21 from the regeneration gas introduction-side switching valves 61 and 64.
The gas discharge passages 26, 27 from the water, oxygen and carbon monoxide removing units 20, 21 are connected to an exhaust passage 28, and gas discharge-side opening/closing valves 62, 63 are provided in the gas discharge passages. Furthermore, regeneration gas recovery devices 52 and 53 are provided for introducing a regeneration gas from regeneration gas supply devices 54 and 55 to the water, oxygen, and carbon monoxide removal unit and recovering the regeneration gas. On the recovery-side passage, on-off valves 57 and 60 for recovering the regeneration gas are disposed.
As the regeneration gas, hydrogen was used as the reducing gas for the nickel catalyst, and dry nitrogen was used for moisture removal of the molecular sieve. Thus, hydrogen and nitrogen were introduced as regeneration gases. Heaters 70 and 71 are provided in the water, oxygen and carbon monoxide removing sections, respectively, for heating treatment during regeneration. As an example of the regeneration treatment, first, while supplying dry nitrogen gas from the regeneration gas supply device 54 or 55 to the water, oxygen, and carbon monoxide removing part and removing moisture for 1 hour, the water, oxygen, and carbon monoxide removing part is heated to about 200 ℃ by the heaters 70 and 71. Next, in this heated state, hydrogen gas was supplied in addition to dry nitrogen gas from the regeneration gas supply device 54 or 55, and reduction treatment of the nickel catalyst was performed for 3 hours. The reduction treatment of the nickel catalyst is performed by the following chemical reaction.
Then, only dry nitrogen gas was supplied, and the adsorbed moisture was removed for 2 hours. Finally, while introducing dry nitrogen gas, the heaters 70 and 71 were gradually reduced in heating, and the temperature was returned to normal temperature over about 5 hours. Further, the regeneration gas is supplied, for example, so that the ammonia purification amount is 3N (standard state) m3In the case of/, the amount of the reduced hydrogen gas may be set to 4N (standard condition) L/h at a dry nitrogen amount of 200N (standard condition) L/h. Further, if the purification is not immediately carried out after the regeneration treatment, the adsorption effect is good if purified ammonia gas is circulated for a certain period of time before the purification.
With the above configuration, since the pair of water, oxygen and carbon monoxide removing units 20 and 21 is used, one can be used for the impurity removing treatment and the other can be subjected to the regenerating treatment. Using a purification control device (not shown), for example, the gas introduction-side valves 56 and 58 are opened from a state where all the valves are closed, and the exhaust-side valve 62 is opened, whereby the crude ammonia is introduced into the water, oxygen, and carbon monoxide removal unit 20. The introduction of the crude ammonia causes removal of oxygen and carbon monoxide impurities by the nickel catalyst in the catalyst section 23, removal of water impurities by adsorption of water by the molecular sieve in the water removal section 22, and discharge of purified ammonia gas obtained by continuous removal of water, oxygen, and carbon monoxide through the exhaust passage 28.
When the purification treatment in the water, oxygen and carbon monoxide removing unit 20 side is completed, the valves 58 and 62 are closed. The valves 59 and 63 are opened again to introduce the crude ammonia into the water, oxygen and carbon monoxide removing section 21, and the purification treatment can be performed subsequently by the catalyst section 25 and the water removing section 24. On the other hand, the water, oxygen and carbon monoxide removing unit 20 which has finished the purification treatment is subjected to the above-mentioned regeneration treatment by opening the valves 57 and 61. By alternately switching the water, oxygen and carbon monoxide removal units to purification and regeneration treatments in this way, it is possible to achieve continuous purification of high-purity ammonia gas by removing impurities of water and oxygen, and to enable large-scale purification.
Hereinafter, a purification apparatus and a purification method thereof capable of efficiently removing a plurality of impurities contained in crude ammonia will be described with reference to fig. 3. FIG. 3 is a schematic configuration diagram of a purification apparatus according to the present embodiment. In this embodiment, the same reference numerals are used for the same components as those in the embodiments of fig. 1 and 2.
The purification apparatus of the present embodiment comprises a distillation column 2 for removing a plurality of non-metallic impurities contained in a crude ammonia gas, and a pair of water, oxygen and carbon monoxide removing sections 20 and 21 for removing impurities such as water, oxygen and carbon monoxide. The distillation column 2 and the water, oxygen, and carbon monoxide removing units 20 and 21 have the same configurations as those described with reference to fig. 1 and 2, respectively. In the present embodiment, the raw ammonia is separated into the liquid phase portion 11 and the gas phase portion 12 in the liquid ammonia container 1, and the gas phase ammonia is discharged from the gas phase portion 12 and introduced into the distillation column 2 as a crude ammonia gas. Reference numeral 19 denotes an on-off valve between the gas phase portion 12 and the gas supply passage 9 and the gas inflow portion 7.
As described above, the distillation column 2 is composed of the distillation section 3, the gas inflow section 7 provided in the middle portion, and the liquefied ammonia storage section 8 provided in the lower portion. Since the non-metallic impurities having a lower boiling point than ammonia are separated as a gas while liquefying the crude ammonia gas by the liquefying function of the distillation section 3 and storing the liquefied ammonia in the liquefied ammonia storage section 8, the impurity gas can be separated and recovered in the uppermost space 6 of the distillation column 2, and a plurality of kinds of impurity gases G1 can be removed at a time by the exhaust gas through the exhaust passage 10. The impurity gas accumulated in the uppermost space 6 is mainly hydrogen (H)2) Oxygen (O)2) Carbon monoxide (CO) and carbon dioxide (CO)2) Nitrogen (N)2) Methane (CH)4) And the like. Further, impurities remaining in the crude ammonia in the distillation section 3 during liquefaction of the crude ammonia are also separated from the liquid ammonia by the heating action of the hot water circulation device 5 provided in the liquefied ammonia storage section 8 provided in the lower part of the distillation column 2, discharged to the gas inflow section 7 side, and finally recovered in the uppermost space 6, whereby the purification purity can be further improved.
The liquid ammonia stored in the liquefied ammonia storage unit 8 is introduced into the water, oxygen and carbon monoxide removing units 20 and 21 through the warm water tank 16 via the discharge passage 14. The liquid ammonia is re-vaporized in the warm water tank 16 and introduced into the water, oxygen and carbon monoxide removing sections 20 and 21 as a secondary purified gas. The water, oxygen, and carbon monoxide removing sections 20 and 21 respectively include a water removing section 22 and a catalyst section 23, and a water removing section 24 and a catalyst section 25. The moisture removing units 22 and 24 remove moisture by adsorption of the filled molecular sieves. The catalyst portions 23 and 25 adsorb and remove oxygen and carbon monoxide by the chemisorption action of the filled nickel catalyst. Therefore, the water, oxygen and carbon monoxide removing units 20 and 21 can further remove the water, oxygen and carbon monoxide impurities which are not treated in the distillation tower 2, and finally, the purified ammonia gas G2 with high purity can be obtained by removing more impurities, particularly water, oxygen and carbon monoxide impurities, from the plurality of impurities through the exhaust passage 28 in two steps.
As described above, the purification apparatus of the present embodiment can realize a more simple purification process by connecting the distillation column 2 to the water, oxygen and carbon monoxide removal units 20 and 21 as a purification system. Further, as described above, since the purification and regeneration are alternately switched using the pair of water, oxygen and carbon monoxide removing units 20 and 21, and one of them can always be subjected to the purification treatment operation, the interruption of the purification treatment during regeneration when the water, oxygen and carbon monoxide removing units 20 and 21 are used can be avoided, and the purification operation can be continued, which contributes to cost reduction of a large amount of purification.
FIG. 4 shows an example of measurement of impurity concentration distribution in which the purification effect of the purification apparatus is exhibited. First, the crude ammonia gas in the gas phase section 12 contains a large amount of hydrogen (H) in ppm concentration unit2) Oxygen (O)2) Carbon monoxide (CO) and carbon dioxide (CO)2) Nitrogen (N)2) Methane (CH)4) Low boiling point impurities of the like and water (H)2O) (see (1) of fig. 4). When the crude ammonia gas is purified by the distillation column 2, water (H) is removed as shown in (3) of FIG. 42O) is reduced to concentration units on the ppb level. Further, since the primary purified gas passed through the distillation column 2 is introduced into the water, oxygen and carbon monoxide removing parts 20 and 21, the concentration of water is also reduced to a ppb level as shown in (4) of FIG. 4. Therefore, by adopting the purification method using the purification apparatus of the present embodiment, purified ammonia having an extremely high purity can be obtained. Further, according to this measurement example, oxygen is substantially removed in the distillation column 2And carbon monoxide impurities, the amount of which is very small at the stages of the water, oxygen and carbon monoxide removing parts 20 and 21.
Further, as shown in fig. 4 (2), although a large amount of moisture is initially contained in the liquid phase, the amount of water in the gas phase ammonia is smaller than that in the liquid phase, but when ammonia is gradually reduced in the course of continuous purification, a phenomenon occurs in which the moisture content in the gas phase is rapidly increased. The measurement of the purification apparatus of this embodiment is exemplified in FIG. 5. As can be seen from fig. 5, when the ammonia usage rate of the liquid ammonia tank 1 reaches about 85%, the moisture in the gas phase increases rapidly. Therefore, the use of about 85% is usually the purification limit, and if the purification apparatus of the present embodiment is used, it can be said that continuous purification is possible to achieve an ammonia utilization of 85%.
As described above, according to the purification method and purification apparatus of the present invention, it is possible to purify industrial raw material ammonia or the like with high purity, and it is possible to simplify the purification step without using a complicated purification step, and it is also possible to easily form a continuous purification step.
Claims (22)
1. A method for purifying a crude ammonia gas containing a low-boiling impurity gas having a boiling point lower than that of ammonia, characterized by introducing the crude ammonia gas into a distillation unit comprising a heat exchanger, liquefying the ammonia gas by the cooling action of the heat exchanger, discharging the low-boiling impurity gas as it is in a gaseous state from the distillation unit, and removing the low-boiling impurity gas from the crude ammonia gas.
2. A method for purifying ammonia gas as defined in claim 1, wherein a liquefied ammonia storage unit for storing liquefied ammonia is provided in the distillation unit, and liquefied ammonia in the liquefied ammonia storage unit is heated to remove low-boiling impurities remaining in the liquefied ammonia by exhausting gas.
3. A method for purifying ammonia gas as defined in claim 1 or 2, wherein the liquefied ammonia is discharged from the liquefied ammonia storage section and passed through a heating section to be vaporized.
4. A method for purifying a crude ammonia gas containing at least water and oxygen, characterized in that the crude ammonia gas is introduced into a water adsorption part for adsorbing water and a catalyst part for separating oxygen, and water and oxygen are removed from the crude ammonia gas.
5. A method for purifying a crude ammonia gas containing at least water and oxygen, characterized in that at least a pair of a water adsorption section for adsorbing water and a catalyst section for separating oxygen is provided, and the crude ammonia gas is introduced into one of the water adsorption section and the catalyst section to remove water and oxygen from the crude ammonia gas, while a reducing gas is introduced into the other of the water adsorption section and the catalyst section to regenerate the crude ammonia gas.
6. An ammonia purification method as defined in claim 5, wherein the purification is continuously performed by alternately repeating the removal of moisture and oxygen from the crude ammonia gas and the regeneration by the introduction of the reducing gas, for each of the pair of the moisture adsorption section and the catalyst section.
7. A method for purifying ammonia gas, which is a method for purifying crude ammonia gas containing water and a low-boiling-point impurity gas having a lower boiling point than ammonia, characterized by comprising a first removal step, a vaporization step and a second removal step, wherein in the first removal step, introducing the crude ammonia gas into a distillation section comprising a heat exchanger, liquefying the ammonia gas by the cooling action of the heat exchanger, discharging the low-boiling impurity gas from the distillation section as it is in a gaseous state, and removing the low-boiling impurity gas from the crude ammonia gas, in the gasification step, ammonia liquefied in the distillation unit is discharged from the distillation unit and gasified by the heating unit, in the second removal step, the ammonia gas vaporized in the vaporization step is introduced into the moisture adsorption section that adsorbs moisture and the catalyst section that separates oxygen, and water and oxygen are removed from the ammonia gas.
8. An ammonia purification method as defined in claim 7, comprising a third removal step of providing a liquefied ammonia storage unit for storing the ammonia liquefied in the first removal step, removing low boiling impurities remaining in the liquefied ammonia by heating the liquefied ammonia in the liquefied ammonia storage unit to discharge the gas, and introducing the liquefied ammonia to the gasification step through the third removal step to gasify the liquefied ammonia.
9. An ammonia purification method as defined in claim 7 or 8, wherein the second removal step comprises a removal process of introducing ammonia gas vaporized in the vaporization step into the moisture adsorption section and the catalyst section provided with at least one of the pair of the moisture adsorption section and the catalyst section to remove water and oxygen from the ammonia gas, and a regeneration process of introducing a reducing gas into the other of the moisture adsorption section and the catalyst section to regenerate the ammonia gas.
10. An ammonia purification method as defined in claim 9, wherein the continuous purification is carried out by alternately repeating the removal treatment of moisture and oxygen and the regeneration treatment by introducing the reducing gas into each of the pair of the moisture adsorbing portion and the catalyst portion.
11. An ammonia gas purification method as defined in any one of claims 1 to 10, wherein the crude ammonia gas is a gas-phase component gas obtained by separating raw ammonia into a liquid phase and a gas phase.
12. An ammonia gas purification apparatus for purifying a crude ammonia gas containing a low-boiling-point impurity gas having a lower boiling point than ammonia, characterized by comprising a distillation unit comprising a heat exchanger for introducing the crude ammonia gas and liquefying the ammonia gas by a cooling action, wherein the distillation unit is provided with an exhaust passage for directly exhausting the low-boiling-point impurity gas in a gaseous state.
13. An ammonia purification apparatus as defined in claim 12, wherein the distillation section comprises a liquefied ammonia storage section for storing liquefied crude ammonia and a heating device for separating the low-boiling impurity gas from the liquefied ammonia in the liquefied ammonia storage section.
14. An ammonia purification apparatus as defined in claim 12 or 13, comprising a vaporizing device for vaporizing the liquefied ammonia discharged from the distillation section.
15. An ammonia gas purification device for purifying a crude ammonia gas containing at least water and oxygen, characterized by comprising a water adsorption section for adsorbing water and a catalyst section for separating oxygen, wherein the crude ammonia gas is introduced into the water adsorption section and the catalyst section to remove water and oxygen from the crude ammonia gas.
16. An ammonia gas purification apparatus for purifying a crude ammonia gas containing at least water and oxygen, comprising at least a pair of a water adsorption section for adsorbing water and a catalyst section for separating oxygen, wherein a crude ammonia gas introduction passage for introducing the crude ammonia gas is provided in each of the water adsorption section and the catalyst section, a reducing gas introduction passage for introducing a reducing gas is provided in each of the water adsorption section and the catalyst section, the crude ammonia gas is introduced into one of the water adsorption section and the catalyst section through the crude ammonia gas introduction passage to remove water and oxygen from the crude ammonia gas, and the reducing gas is introduced into the other of the water adsorption section and the catalyst section through the reducing gas introduction passage to regenerate the crude ammonia gas.
17. An ammonia purification apparatus as defined in claim 16, comprising a continuous purification control unit for controlling opening and closing of the crude ammonia gas introduction passage and the reducing gas introduction passage, wherein the moisture and oxygen of the crude ammonia gas are removed and the reducing gas is introduced into each of the pair of the moisture adsorption unit and the catalyst unit, alternately and repeatedly.
18. An ammonia gas purification apparatus for purifying a crude ammonia gas containing water and a low-boiling-point impurity gas having a boiling point lower than that of ammonia, characterized by comprising a distillation unit comprising a heat exchanger for liquefying ammonia gas by a cooling action after introducing the crude ammonia gas, an exhaust passage provided in the distillation unit for directly exhausting the low-boiling-point impurity gas in a gaseous state, a vaporizer for vaporizing the liquefied ammonia discharged from the distillation unit, a moisture adsorption unit for adsorbing moisture, a catalyst unit for separating oxygen, and an ammonia gas introduction passage for introducing the ammonia gas vaporized by the vaporizer into the moisture adsorption unit and the catalyst unit.
19. An ammonia purification apparatus as defined in claim 18, wherein a liquefied ammonia storage unit for storing crude ammonia liquefied in the distillation unit is provided in the distillation unit, and the liquefied ammonia storage unit has a heating device for separating low-boiling impurities from liquefied ammonia remaining in the liquefied ammonia storage unit.
20. An ammonia purification apparatus as defined in claim 18 or 19, comprising at least one pair of the moisture adsorption section and the catalyst section, wherein the ammonia gas introduction passage for introducing the ammonia gas gasified by the gasification apparatus is provided in each of the moisture adsorption section and the catalyst section, and a reducing gas introduction passage for introducing a reducing gas is provided in each of the moisture adsorption section and the catalyst section, wherein the gasified ammonia gas is introduced into one of the moisture adsorption section and the catalyst section through the ammonia gas introduction passage to remove water and oxygen from the ammonia gas, while the reducing gas is introduced into the other of the moisture adsorption section and the catalyst section through the reducing gas introduction passage to regenerate the ammonia gas.
21. An ammonia purification apparatus as defined in claim 20, comprising a continuous purification control unit for controlling opening and closing of the ammonia introduction passage and the reducing gas introduction passage so that the removal of moisture and oxygen from the crude ammonia gas and the regeneration by the introduction of the reducing gas are alternately repeated for each of the pair of the moisture adsorption unit and the catalyst unit.
22. An ammonia gas purification apparatus as defined in any one of claims 12 to 21, wherein the crude ammonia gas is a gas-phase component gas obtained by separating raw ammonia into a liquid phase and a gas phase.
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| Application Number | Priority Date | Filing Date | Title |
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| JP2003404852 | 2003-12-03 | ||
| JP2003404852A JP4062710B2 (en) | 2003-12-03 | 2003-12-03 | Method and apparatus for purifying ammonia |
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| CN1623900A true CN1623900A (en) | 2005-06-08 |
| CN1330573C CN1330573C (en) | 2007-08-08 |
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| CNB2004100617629A Expired - Fee Related CN1330573C (en) | 2003-12-03 | 2004-06-30 | Refining method and device for ammonia |
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| JP (1) | JP4062710B2 (en) |
| KR (1) | KR100650010B1 (en) |
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| CN102145899A (en) * | 2010-02-05 | 2011-08-10 | 跨特株式会社 | Producing method and device of high purity ammonia |
| CN102464341A (en) * | 2010-11-02 | 2012-05-23 | 住友精化株式会社 | System for purifying ammonia |
| CN103153861A (en) * | 2011-01-25 | 2013-06-12 | 住友精化株式会社 | Ammonia purification system and method for purifying ammonia |
| CN103269980A (en) * | 2011-03-31 | 2013-08-28 | 住友精化株式会社 | Method for purifying ammonia and ammonia purification system |
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| IL70596A (en) * | 1984-01-02 | 1987-11-30 | Israel State | Level based on moire effect with ambient light |
| JPH09142883A (en) * | 1995-11-17 | 1997-06-03 | Central Glass Co Ltd | Radio wave transmitting heat-shielding glass and its production |
-
2003
- 2003-12-03 JP JP2003404852A patent/JP4062710B2/en not_active Expired - Fee Related
-
2004
- 2004-04-27 TW TW093111722A patent/TWI261574B/en not_active IP Right Cessation
- 2004-04-27 KR KR1020040029027A patent/KR100650010B1/en active IP Right Grant
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| CN102145899A (en) * | 2010-02-05 | 2011-08-10 | 跨特株式会社 | Producing method and device of high purity ammonia |
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Also Published As
| Publication number | Publication date |
|---|---|
| CN1330573C (en) | 2007-08-08 |
| JP4062710B2 (en) | 2008-03-19 |
| KR100650010B1 (en) | 2006-11-24 |
| TWI261574B (en) | 2006-09-11 |
| JP2005162546A (en) | 2005-06-23 |
| KR20050053474A (en) | 2005-06-08 |
| TW200519039A (en) | 2005-06-16 |
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Owner name: TAIYO NIPPON SANSO CO., LTD. Free format text: FORMER NAME OR ADDRESS: DAIYO TOYO ACID CO., LTD. |
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Address after: Tokyo, Japan Patentee after: Daiyo Acid Co., Ltd. Address before: Osaka Japan Patentee before: Taiyo Toyo Sanso K. K. |
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Granted publication date: 20070808 Termination date: 20210630 |
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